JP2006161170A - Oil agent for synthetic fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil agent having a low production cost as compared with conventional oil agents by using an ester compound obtained by a reaction by using a new catalyst having a high activity, and also capable of obtaining a yarn having stable productivity and quality. <P>SOLUTION: This oil agent for the synthetic fiber is characterized by containing (A) the ester compound obtained by reacting (a1) a carboxylic acid and/or (a2) an ester-forming derivative with (b) an alcohol by using (c) a metal complex formed by (c1) a chelating agent with (c2) a titanate compound as a catalyst, (B) an emulsifying agent component and (C) a moistening component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an oil for synthetic fibers. More specifically, the present invention relates to a synthetic fiber oil used in a synthetic fiber spinning process.

In the synthetic fiber manufacturing process, an oil agent for synthetic fiber (hereinafter simply referred to as an oil agent) that imparts lubricity, bundling property, antistatic property, etc. to the fiber is used in order to facilitate fiber spinning and drawing. . In recent years, with the increase in spinning speed, there has been a demand for an oil agent with less occurrence of yarn breakage, fluff and the like in the spinning process. In order to impart lubricity to oil agents, esters, particularly fatty acid esters, are often used as lubricants.
Conventionally, paratoluenesulfonic acid, a sulfuric acid catalyst, etc. are used as an esterification catalyst for synthesizing these esters. However, if these catalysts are used as an oil agent with the catalyst remaining, not only will there be a lot of yarn breakage or fluffing in the spinning process due to poor heat resistance or coloration derived from the catalyst, but also the quality of the yarn after spinning. Also adversely affects. Therefore, in order to use as an oil agent, the catalyst removal process of neutralizing with alkaline aqueous solution after esterification and filtering the produced | generated neutralized salt was essential. However, even if such a catalyst removal step is performed, the catalyst remaining in a trace amount has an adverse effect on lubricity and heat resistance under the spinning conditions that have been increased in recent years, thereby deteriorating the spinning performance.
In order to solve these problems, a method using a solid acid catalyst such as an ion exchange resin has been proposed as a method for preventing the catalyst from remaining in the ester compound in esterification. (For example, Non-Patent Document 1)
Catal Lett Vol. 78, No1 / 4; 185-188 (2002)

However, the methods using these solid acid catalysts are not practical because they require a long time for the esterification reaction. In addition, if a large amount of catalyst is used, a part of the catalyst is dissolved in the ester compound, which also adversely affects the spinning process and yarn quality.
In addition to this, after performing esterification using a normal catalyst, removing the catalyst several times or for a long time can reduce the effect of the remaining catalyst, but the cost increases by performing many removal steps. It is hard to say that it is practical. Furthermore, a method of performing esterification without using a catalyst is conceivable, but this is not practical because the reaction requires a very long time.
The object of the present invention is to use an ester compound obtained by reacting with a highly active novel catalyst that does not affect the yarn-making property, thereby making it possible to lower the production cost compared with conventional oil agents and It is to provide an oil agent that can yield a yarn having less yarn breakage and fluff in the spinning process and having a stable quality as compared with an oil agent using a kind.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by using, as a lubricant, an ester compound produced using an organometallic compound having a specific structure as an esterification reaction catalyst. The present invention has been reached.
That is, the present invention uses a metal complex (c) formed from a chelating agent (c1) and a titanate compound (c2) as a catalyst, and a carboxylic acid (a1) and / or an ester-forming derivative (a2) and an alcohol ( An oil for synthetic fibers characterized by containing an ester compound (A) obtained by reacting b) with an emulsifier component (B) and a wetting component (C).

  The oil agent of the present invention can reduce the production cost as compared with conventional oil agents, and the ester compound (A) does not have a catalyst residue that causes deterioration in heat resistance, and thus has good heat resistance in the yarn production process, Further, the combination of the emulsifier component (B) and the wet component (C) has the effect of imparting good yarn-making properties in the spinning process and enabling the production of high-quality yarn.

First, the metal complex (c) in the present invention will be described.
(C) in this invention will not be specifically limited if it is a complex formed from a chelating agent (c1) and a titanate compound (c2).

  A known chelating agent can be used as the chelating agent (c1). For example, phosphorus chelating agents (sodium pyrophosphate, sodium tripolyphosphate, potassium trimetaphosphate, sodium tetrametaphosphate, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), amine chelating agents (ethylenediamine, triethylenediamine, Tetraethylenetriamine, dimethylglyoxime, 8-oxyquinoline, porphyrin, etc.), aminocarboxylic acid-based chelating agents [ethylenediamine diacetic acid and its metal salts (metal is sodium, potassium, etc.) neutralized, ethylenediaminetetraacetic acid and its Metal salt neutralized product, hexylenediamine diacetic acid and its metal salt neutralized product, hydroxyethyliminodiacetic acid and its metal salt neutralized product, nitrilotriacetic acid trisodium, hydroxyethylethylenediaminetriacetic acid trisodium , Diethylenetriaminepentaacetic acid pentasodium salt, triethylenetotolamine hexaacetic acid hexasodium salt, dihydroxyethylglycine, glycine, L-glutamic acid diacetic acid tetrasodium salt, etc.], carboxylic acid chelating agents (oxalic acid, disodium maleate, ethylenedicarbon Acid, adipic acid, sebacic acid, gluconic acid, sodium gluconate, etc.), ketone chelating agents (acetylacetone, hexane-2,4-dione, 3-ethylnonane-4,7-dione, etc.), polymer chelating agents (Sodium polyacrylate, poly [sodium 2-hydroxyacrylate] and the like). Of these, amine-based chelating agents, aminocarboxylic acid-based chelating agents, carboxylic acid-based chelating agents, and ketone-based chelating agents are preferable, and aminocarboxylic acid-based chelating agents and carboxylic acids are more preferable. A chelating agent and a ketone chelating agent.

When the metal complex (c) is used as a catalyst, the chelating agent (c1) is preferably a compound represented by the following general formula (1) from the viewpoint of stability during the reaction.
[Wherein, X is a group represented by -OM or a hydrocarbon group having 1 to 30 carbon atoms, and some of the hydrogen atoms may be substituted with halogen atoms; M is a hydrogen atom or an alkali Metal atom; Y is a C1-C14 hydrocarbon group which may contain a nitrogen atom; X may be the same or different.

  In general formula (1), X is a group represented by -OM or a hydrocarbon group having 1 to 30 carbon atoms, and a part of the hydrogen atoms may be substituted with a halogen atom. M is a hydrogen atom or an alkali metal atom. Examples of the alkali metal atom include sodium, potassium, rubidium, and cesium. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. From the viewpoint of reactivity as a catalyst, X is preferably a hydrocarbon group not substituted with —OH or a halogen atom, more preferably —OH, an alkyl group, and an alkenyl group, and particularly preferably —OH and An alkyl group is most preferred, -OH and an alkyl group having 1 to 18 carbon atoms.

Specific examples of the hydrocarbon group constituting X include the following groups, but are not limited thereto.
(1) an alkyl group;
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decanyl, dodecanyl, tetradecanyl Group, hexadecanyl group, octadecanyl group, 1,1,1-trifluoromethyl group, 1-monochloroethyl, 2-monofluorononyl group, 4,4-dichlorooctyl group and the like.
(2) an alkenyl group;
Octadecenyl group, 10,10,10-trichlorodecenyl group and the like.
(3) a cycloalkyl group;
A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopropyl group, a cyclohexyl group, a cycloheptyl group, and the like.
(4) a cycloalkenyl group;
A cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclododecenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like.
(5) an aryl group;
Phenyl group, tolyl group, xylyl group, cumyl group, mesyl group, 1-ethylphenyl group, 2-propylphenyl group, 1-tertiarybutylphenyl group, 1,3,5-trimethylphenyl group, 3-hexylphenyl group 3-octylphenyl group, 3-nonylphenyl group, 3-decylphenyl group, 5-dodecylphenyl group, 3-phenylphenyl group, 3-benzylphenyl group, p-cumylphenyl group and the like.
X may be the same or different.

  In general formula (1), Y is a C1-C14 hydrocarbon group which may contain a nitrogen atom, and in addition to the C1-C14 hydrocarbon group exemplified in X above, An alkyl group having 1 to 14 carbon atoms, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, etc. having one or more amino groups, nitrile groups, nitro groups, urea groups, urethane groups, etc. can give. Among Y, from the viewpoint of reactivity as a catalyst, a hydrocarbon group having 1 to 10 carbon atoms, an amino group, a nitrile group, and a nitro group is preferred, and a hydrocarbon having 1 to 10 carbon atoms. More preferred is a hydrocarbon group having a group and an amino group.

  Specific examples of the chelating agent (c1) include ethylenediamine diacetate, hexylenediaminediacetic acid, ethylenedicarboxylic acid, adipic acid, sebacic acid, propylene diacetylamide, ethylene dioctanamide, acetylacetone, hexane-2,4- Examples thereof include, but are not limited to, dione and 3-ethylnonane-4,7-dione.

The titanate compound (c2) constituting the metal complex (c) is not particularly limited. For example, titanium halide (titanium tetrachloride, titanium tetrafluoride, oxychloride titanate, etc.), titanate (disodium titanate, calcium titanate, etc.), titanium alkoxide (tetramethoxy titanate, tetraethoxy titanate, tetraisopropoxy) Titanate, tetrabutoxy titanate, etc.).
From the viewpoints of stability and activity during the reaction of the metal complex (c) as a catalyst, the titanate compound (c2) is preferably a compound represented by the following general formula (2).
[In Formula (2), L is a group represented by R ¹ , R ¹ O— or R ¹ S—, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, and some of the hydrogen atoms are halogen atoms. May be replaced with]

In general formula (2), L is a group selected from the group consisting of R ¹ , R ¹ O— or R ¹ S—, and is preferably R ¹ or R ¹ O— from the viewpoint of reactivity. From the viewpoint of reactivity with the chelating agent (c1), R ¹ O— is most desirable. R ¹ is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group, and some of the hydrogen atoms are halogen atoms. May be substituted. Of R ¹ , an alkyl group and an alkenyl group are preferable, an alkyl group is more preferable, and an alkyl group having 2 to 18 carbon atoms is most preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of reactivity as a catalyst, the halogen atom is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Specific examples of R ¹ include the same examples as given in the illustration of X.

  The metal complex (c) is formed from the chelating agent (c1) and the titanate compound (c2) as shown above. The method for obtaining (c) is not particularly limited, and a known method can be used. For example, methods described in detail in New Experimental Chemistry Course 12 (Organic Metal Chemistry) [Maruzen Publishing], Experimental Science Course 4th Edition 17 (Inorganic Complexes, Chelate Complexes) [Maruzen Publishing] and the like can be mentioned. Specifically, for example, titanium tetrachloride, titanium alkoxide (e.g., methoxide, ethoxide, etc.) is added dropwise to a chelating agent such as ethylenediaminediacetic acid or acetylacetone at 20 to 100 ° C., and the generated hydrochloric acid or alcohol is reduced in pressure. It is obtained by the method of removing by The ratio (molar ratio) between (c1) and (c2) is not particularly limited, but is preferably (c1) / (c2) = 1/4 to 4/1 from the viewpoint of activity as a catalyst. More preferably, (c1) / (c2) = 1/3 to 3/1, and most preferably (c1) / (c2) = 1/2 to 2/1.

  Specific examples of the metal complex (c) include the following, but are not limited thereto. For example, diethoxy titanate-bis (butanedioic acid) complex, diethoxy titanate-bis (adipic acid) complex, tetra (sebacic acid) titanate complex, diisopropoxy titanate-bis (acetylacetone) complex, dioctoxy titanate-bis (Tetradec-5,10-dione) complex, tetra (octadecanoxy) titanate- (2-methyloctadeca-3,8-dione) complex, diethoxytitanate-bis (ethylenediaminediacetic acid) complex, dibutoxytitanate-bis ( Ethylenediaminediacetic acid) complex, diisopropoxytitanate-bis (hexylenediaminediacetic acid) complex, tetrabutoxytitanate-ethylenedioctanamide complex, diethoxytitanate-bis (methylenedipropylamide) complex, and the like.

  When the metal complex (c) is used as a catalyst for esterification reaction, it may be used alone or in combination of two or more. The amount of (c) used is not particularly limited, but is usually 0.0005 to 2 parts by weight, preferably 0.001 to 100 parts by weight per 100 parts by weight of the carboxylic acid component (a1) or carboxylic acid derivative component (a2) in the production of the ester. 1 part by weight, more preferably 0.002 to 0.8 part by weight. Moreover, you may use together the other catalyst well-known in the esterification technique in the range which does not inhibit performance. Other known catalysts include acid catalysts such as para-toluenesulfonic acid and sulfuric acid; antimony catalysts such as antimony trioxide; tin catalysts such as monobutyltin oxide; titanium catalysts such as tetrabutyl titanate; Zirconium-based catalysts such as Kone 卜; acetate metal salt-based catalysts such as zirconyl acetate and zinc acetate; alkali catalysts such as sodium hydroxide and potassium hydroxide. These known catalysts may be used in combination of two or more. The blending ratio when other catalyst is used in combination with (c) is not particularly limited, but is preferably (c) / other catalyst = 1/1 to 1 / 0.01, more preferably 1 / 0.5 in weight ratio. ~ 1 / 0.05.

  The ratio of the carboxylic acid (a1) and / or the ester-forming derivative (a2) to the alcohol (b) in the esterification is not particularly limited, but is usually a molar ratio (carboxylic acid and / or ester-forming derivative thereof). / Alcohol = 4/1 to 1/4, preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1 / 1.5.

The ester compound (A) constituting the present invention is obtained by esterifying the carboxylic acid (a1) and / or its ester-forming derivative (a2) with the alcohol (b) using the metal complex (c) as a catalyst. can get.
The production method (esterification method) for obtaining (A) is not particularly limited, and a known method can be used. For example, (a1) and / or (a2) and (b) can be obtained by a method in which a predetermined amount of each is charged into a reaction tank, a catalyst is added and then heated, and water generated or alcohol generated by transesterification is removed. It is done. The reaction temperature is usually 50 to 280 ° C, preferably 80 to 250 ° C, more preferably 100 ° C to 230 ° C. The reaction time is usually 5 to 20 hours. Removal of water generated by esterification or alcohol generated by transesterification may be performed under normal pressure or reduced pressure. When the removal is performed under reduced pressure, the degree of reduced pressure is preferably 30 mPa or less. The progress of the reaction can be usually determined by measuring the acid value, the hydroxyl value and the like.

  Further, in the esterification reaction for obtaining the ester compound (A), an anti-coloring agent, a stabilizer (such as a phosphate ester), a filler (such as silica or titanium oxide) as a regulator, or a coloring agent, if necessary. (Carbon black, dye, etc.), oxidation stabilizer (hydroquinone, etc.), etc. may be used.

  Specific examples of the carboxylic acid (a1) and its ester-forming derivative (a2) include the following, but are not limited thereto. The ester-forming derivative (a2) is a carboxylic acid halide, a carboxylic acid anhydride, a lower (carbon number 1 to 4) alcohol ester of a carboxylic acid, or the like.

(Aa1); an aliphatic monocarboxylic acid having 2 to 32 carbon atoms and an ester-forming derivative thereof such as butanoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, palmitic acid, stearic acid , Isostearic acid, isoarachidic acid, acrylic acid, oleic acid, erucic acid, methyl octoate, isopropyl laurate, methyl stearate, methyl oleate and the like.
(Aa2); C2-C40 aliphatic dicarboxylic acid and its ester-forming derivatives such as malonic acid, succinic acid, adipic acid, elaidic acid, maleic acid, fumaric acid, 3,3-dimethylpentanedioic acid, adipine Dimethyl acid, maleic anhydride and the like.
(Aa3); C4-42 aliphatic polycarboxylic acid and ester-forming derivatives thereof, 3,3-dimethyl-5-ethyloctane-1,2,8-tricarboxylic acid and the like.

(Aa4); an aromatic carboxylic acid having 7 to 36 carbon atoms and an ester-forming derivative thereof such as benzoic acid, phenylacetic acid, γ-phenylbutyric acid, m-toluic acid, 3-phenylbutanoic acid, phthalic acid, anisic acid, Methyl benzoate, phthalic anhydride, trimellitic acid, etc.
(Aa5); other carboxylic acids and ester-forming derivatives thereof, such as cyclohexanecarboxylic acid, thiodipropionic acid, thiodihexanoic acid, oxypivalic acid, dimethyl thiodipropionate, and the like.

  Of these carboxylic acids and ester-forming derivatives thereof, preferred are aliphatic monocarboxylic acids having 2 to 32 carbon atoms and ester-forming derivatives thereof (aa1), aliphatic dicarboxylic acids having 2 to 40 carbon atoms and ester formation thereof. Derivative (aa2), and C4-42 aliphatic polycarboxylic acid and its ester-forming derivative (aa3), more preferably (aa1) and (aa2), and (aa1) is most preferable. . The carboxylic acid (a1) or its ester-forming derivative (a2) may be used in combination of two or more, or (a1) and (a2) may be used in combination.

Examples of alcohol (b) include, but are not limited to, (bb1); aliphatic monohydric alcohols having 4 to 32 carbon atoms such as octyl alcohol, 2 -Ethylhexyl alcohol, lauryl alcohol, palmityl alcohol, t-butyl alcohol, isostearyl alcohol, allyl alcohol, methyl vinyl carbinol, oleyl alcohol and the like.
(Bb2); C3-C40 aliphatic polyvalent (2-6 valent) alcohols such as 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.

(Bb3); C6-C36 alicyclic alcohols such as cyclopentanol, cyclohexanol, 3-butyl-5-octylcyclooctanol, 3-ethylcyclohexanol, cis-1,2-cyclohexanediol, etc. .
(Bb4); C7-36 aromatic alcohols such as benzyl alcohol, 2-phenylethanol, α-phenylethyl alcohol, triphenylcarbinol, cinamyl alcohol and the like.
(Bb5); alkylene oxide adducts (addition mole number 1 to 100) and other alkylene oxide adducts (addition mole number 1 to 100) of the above (bb1) to (bb4), for example, 10 moles of ethylene oxide of lauryl alcohol Adduct, propylene oxide 5 mol adduct of oleyl alcohol, ethylene oxide 3 mol adduct of glycerin, propylene oxide 50 mol adduct of benzyl alcohol, ethylene oxide 5 mol of stearic acid, propylene oxide 5 mol adduct, phenol ethylene 20 mol adduct of oxide, 4 mol adduct of bisphenol A and ethylene oxide, etc.

  Examples of the alkylene oxide (hereinafter abbreviated as AO) in (bb5) include AO having 2 to 12 carbon atoms, specifically ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), Examples include butylene oxide (hereinafter abbreviated as BO), tetrahydrofuran (hereinafter abbreviated as THF), styrene oxide (hereinafter abbreviated as SO), and the like. A known method can be applied as a method for adding these AOs. For example, an AO adduct can be obtained by adding AO to a compound having active hydrogen in the presence of a catalyst. The reaction temperature is usually 10 to 180 ° C., and the reaction time is 1 to 48 hours. AO may be used alone or in combination of two or more. When two or more types of AO are added, the addition mode is not particularly limited, and may be added randomly or added to a block. Catalysts used for adding AO include alkali catalysts (potassium hydroxide, sodium hydroxide, etc.), hydrotalcite catalysts (trade name: KW500SH, manufactured by Kyowa Chemical Industry Co., Ltd.), acidic catalysts (peroxide, etc.). Halogen acid (salt), sulfuric acid (salt), phosphoric acid (salt) and nitric acid (salt), and metal alcoholate catalysts (sodium methylate, potassium butyrate, etc.). Two or more of these catalysts may be used in combination. The amount of these catalysts added is usually 0.01 to 8% by weight based on the total weight after AO addition.

  Of these alcohols (b), the aliphatic alcohol (bb1) is preferable, and the aliphatic monohydric alcohol is more preferable. Moreover, (b) may be used in combination of two or more.

Specific examples of the ester compound (A) include the following, but are not limited thereto.
(A1); monovalent ester compounds, for example, 2-ethylhexyl stearate, isodecyl stearate, isostearyl oleate, isoeicosyl stearate, isoeicosyl oleate, isotetracosyl oleate, isoarachidyl oleate, isostearyl Palmitate, oleyl oleate, lauryl isostearate, lauric acid ester of lauryl alcohol EO 2 mol adduct, stearic acid ester of oleyl alcohol PO 2 mol adduct, and the like.
(A2); divalent ester compounds such as glycerin dioleate, pentaerythritol tetraoleate, dioleyl adipate, diisotridecyl adipate, stearyl alcohol EO 10 mol adduct diester, bisphenol EO 5 mol adduct dioleic acid Esters etc.
(A3); polyvalent ester compounds such as glycerin trioleate, sorbitol tetrastearate, trimellitic acid trilaurate and the like.
(A4); Other esters such as dilauryl thiodipropionate, dioleyl thiodipropionate, diisostearyl thiodipropionate, and the like.

  Of these ester compounds (A), the monovalent ester (A1) or the divalent ester (A2) is preferred, the monovalent ester (A1) is more preferred, and the monovalent ester having no AO chain Most preferably (A1). Moreover, (A) may be used in combination of two or more.

Next, the emulsifier component (B) will be described.
The emulsifier component (B) is a surfactant having an emulsifying function, which is a nonionic surfactant (such as an AO adduct of a higher alcohol), an anionic surfactant (a higher alcohol sulfate Na salt, alkyl sulfonate Na salt). Etc.), cationic surfactants (alkylamines and metal salts thereof) and amphoteric surfactants (betaine-type amphoteric surfactants, amino acid-type surfactants, etc.). Among these, (B) is preferably a nonionic surfactant, and has a weight average molecular weight (hereinafter abbreviated as Mw) 1,000 or more having a polyalkylene glycol (hereinafter abbreviated as PAG) chain in the molecule. The PAG type nonionic surfactant (B1) is more preferable. The PAG possessed by (B1) can be obtained by adding AO to a compound having active hydrogen. As a method for adding AO, a known method can be used, and a specific method or the like is the same as the method exemplified in the explanation of (bb5). The AO that forms the PAG is not particularly limited, but EO alone or a combination of EO and PO is preferred. When EO and PO are used in combination, the addition mode (random or block) and the constituent weight ratio of EO and PO are not particularly limited, but the weight ratio of EO is preferably 50% or more.

  The Mw of the PAG-type nonionic surfactant (B1) is 1,000 to 30,000, preferably 1,200 to 25,000, more preferably from the viewpoint of stability and smoothness after blending the oil agent. Is 1,500 to 20,000.

Specific examples of the PAG type nonionic surfactant (B1) include the following.
(B11); AO adduct of aliphatic alcohol having 4 to 36 carbon atoms (Mw = 1,000 or more), for example, butanol EO 20 mol PO 10 mol block adduct, butanol EO / PO random adduct (Mw = 2,000) ), N-octyl alcohol EO 30 mol adduct, oleyl alcohol EO 20 mol adduct, isostearyl alcohol EO 10 mol adduct, stearyl alcohol EO / PO random adduct (Mw = 2,000), neopentyl glycol EO 30 mol adduct, Sorbitol EO 40 mole adduct and the like.
(B12); AO adduct of alicyclic alcohol having 6 to 42 carbon atoms (Mw = 1,000 or more), for example, cyclohexanol EO 25 mol adduct, 3-ethylcyclohexanol EO / PO random adduct (Mw = 1,500), trans-1,2-cyclohexanol EO 45 mol adduct and the like.
(B13); AO adduct of aromatic alcohol having 7 to 40 carbon atoms (Mw = 1,000 or more), for example, benzyl alcohol EO 25 mol adduct, octylphenol EO 20 mol adduct, nonylphenol EO 25 mol adduct, dodecylphenol EO100 Mole adduct etc.
(B14); AO adduct of fatty acids having 4 to 40 carbon atoms (Mw = 1,000 or more), for example, oleic acid EO 20 mol adduct, stearic acid EO / PO random adduct (Mw = 3,000) and the like.
(B15): AO adducts of phenol and phenol derivatives (Mw = 1,000 or more), for example, phenol EO 20 mol adduct, bisphenol A PO 10 mol, EO 30 mol block adduct, etc.
(B16); AO adduct of polyvalent (2 to 8 valent) alcohol fatty acid ester (Mw = 1,000 or more), for example, EO 40 mol adduct of glycerin monostearate, castor oil EO 10 mol adduct, castor oil EO / PO random adduct (Mw = 3,000), hydrogenated castor oil EO 40 mol adduct, hydrogenated castor oil EO 10 mol PO 25 mol adduct, sorbitan monooleate EO 20 mol adduct, etc.

  Among these, preferred are AO adducts (B11) of aliphatic alcohols having 4 to 36 carbon atoms with Mw = 1,000 or more, AO adducts (B13) of aromatic alcohols having 7 to 40 carbon atoms, and many An AO adduct (B16) of a divalent (2 to 8 valent) alcohol fatty acid ester, more preferably (B11) and (B16). The emulsifier component (B) may be used in combination of two or more.

Next, the wet component (C) will be described.
(C) is a functional agent that imparts wettability to the synthetic fiber to the oil, and nonionic surfactants, anionic surfactants, and the like that impart wettability can be used. It is preferable that the aliphatic alcohol AO adduct (C1) has an Mw of less than 1,000. AO having 2 to 12 carbon atoms can be used, and the method for adding AO is the same as described above. As AO, EO alone or a combination of EO and PO is preferable, and EO alone is more preferable. When EO and PO are used in combination, the addition mode (random addition or block addition) is not particularly limited, but is preferably a block adduct, and the constituent weight ratio of EO and PO is not particularly limited. It is more preferable that the weight ratio of is 70% or more.

Specific examples of the aliphatic alcohol AO adduct (C1) having an Mw of less than 1,000 include the following, but are not limited thereto.
(C11); C8-22 linear aliphatic alcohol AO adduct (Mw = less than 1,000), for example, octyl alcohol EO 8 mol adduct, decyl alcohol EO 10 mol, PO2 mol adduct, lauryl alcohol EO 10 mol Additives, oleyl alcohol EO 5 mol adduct, stearyl alcohol PO 2 mol, EO 2 mol adduct, etc.
(C12); branched aliphatic alcohol AO adduct having 8 to 22 carbon atoms (Mw = less than 1,000), for example, 2-ethylhexyl alcohol PO5 mol EO5 mol adduct, isodecyl alcohol EO2 mol adduct, isotridecyl Alcohol EO 10 mol adduct, isostearyl alcohol PO 4 mol, EO 1 mol adduct, etc.
Among these, preferred are branched aliphatic alcohol AO adducts (C12) having 8 to 22 carbon atoms, more preferred are branched aliphatic alcohol AO adducts having 10 to 18 carbon atoms, Most preferred is a 16 branched aliphatic alcohol AO adduct.
In addition, (C) may be used in combination of two or more.

  The oil agent of the present invention contains the ester compound (A), the emulsifier component (B) and the wet component (C) described above as essential components, but it is preferable that each component is further contained in a specific ratio.

  That is, the ratio ((A) / [(B) + (C)]) of the total weight of the ester compound (A), the emulsifier component (B) and the wet component (C) is 3/1 to 1/3, and ( The weight ratio of (B) to (C) ((B) / (C)) is 4/1 to 1/6, and the weight of (A) is the total weight of the oil ((A) + (B) + (C ) + 5 to 80% by weight based on the other components (D) described later). More preferably, the ratio of the total weight of (A) and (B) and (C) ((A) / [(B) + (C)]) is 2.5 / 1 to 1 / 2.5, and ( The weight ratio of B) to (C) ((B) / (C)) is 3.5 / 1 to 1/5, and the weight of (A) is 7 to 78% by weight based on the total weight of the oil. is there. When (A), (B), and (C) are in this range, smoothness and wettability are further improved, and the yarn-making property tends to be improved.

The oil agent of the present invention may contain other component (D) as necessary. Examples of (D) include the following. (D) may be used in combination of two or more.
(D1); lubricants other than (A), for example, mineral oil having a kinematic viscosity at 25 ° C. of 10 to 3,000 cSt (for example, refined spindle oil having a kinematic viscosity at 25 ° C. of 200 cSt, kinematic viscosity at 25 ° C.) Such as liquid paraffin, etc.), animal and vegetable oils (eg beef tallow, sperm whale oil, rapeseed oil, coconut oil, castor oil etc.), silicone compounds (eg dimethylpolysiloxane, amino-modified silicone, phenyl-modified silicone etc.), natural and Synthetic waxes (for example, carnauba wax, beeswax, paraffin wax having a melting point of 30 ° C. to 100 ° C. and polyolefin wax [olefin having 2 to 18 carbon atoms, Mw = 1,000 to 10,000 wax, for example, polyethylene wax]) and the like.

(D2); surfactants other than (B) and (C), such as fatty acid alkanolamides (oleic acid diethanolamide, stearic acid monoisopropanolamide, etc.), alkylamines having 6 to 32 carbon atoms, and those having 2 carbon atoms -4 AO adducts (for example, 1 to 40 moles added) (for example, triethylamine, laurylamine EO 1 mol adduct, stearylamine EO 7 mol adduct, etc.) and the like.

(D3); Antistatic agents, for example, phosphates (for example, phosphate esters of lauryl alcohol) of alcohols having 8 to 32 carbon atoms and these AO adducts having 2 to 4 carbon atoms (for example, 1 to 20 moles added) Potassium salt, phosphate ester sodium salt of EO 2 mol adduct of stearyl alcohol, phosphate ester potassium salt of EO 7 mol adduct of isostearyl alcohol), (thio) phosphite having 9 to 90 carbon atoms (for example, triphenyl) Phosphite, trilauryl trithiophosphite, etc.), fatty acid soap having 8 to 32 carbon atoms (counter ions are, for example, ammonium, sodium, potassium, ammonia, etc.) (eg, ammonium laurate soap, potassium oleate soap, castor oil sodium) Soap, etc.), imidazoline compounds having 8 to 32 carbon atoms For example, lauryl imidazoline, oleyl imidazoline, etc.), sulfates having 8 to 32 carbon atoms and salts thereof (for example, lauryl alcohol sulfate sodium salt, ammonium oleyl alcohol sulfate), sulfonic acids having 8 to 32 carbon atoms and the like Salts (eg, lauryl sulfonate sodium salt, dodecylbenzene sulfonic acid and its sodium salt, sulfosuccinic acid di-2-ethylhexyl ester sodium salt, etc.) and the like.

(D4); antioxidant, for example, hindered phenol antioxidant (2,6-di-t-butylphenol, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy Phenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), amine antioxidant (2,4-bis- (n-octylthio) ) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like).

(D5); UV absorber, for example, benzotriazole (2- (3,5-di-t-amyl) hydroxyphenyl etc.), hindered amine (bis (2,2,6,6-tetramethyl-4-) Piperidyl) sebacate, etc.).

(D6); Fluorine compound, for example, perfluoroethane, perfluorooctane and the like.
(D7); pH adjusters such as hydrochloric acid, hypophosphorous acid, phosphoric acid, hydrochloric acid, sulfuric acid, lower fatty acids (2 to 8 carbon atoms) and derivatives thereof (for example, acetic acid, lactic acid, malic acid, sodium acetate, etc.) , Ammonia and alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide), higher fatty acids (lauric acid, oleic acid, stearic acid, salicylic acid, penta Decenyl succinic acid) and the like.
(D8); Other additives such as appearance modifiers (ethylene glycol, propylene glycol, oleyl alcohol, etc.), water, and the like.
When using other component (D), it is preferable that a compounding quantity (weight%) is 0.01 to 50 weight% with respect to the total weight of an oil agent.

  The oil agent of this invention can be obtained by mix | blending ester compound (A), an emulsifier component (B), a wet component (C), and another component (D) as needed. The blending method is not particularly limited, and a known method can be applied. For example, it is possible to use a method in which a predetermined amount of each component is charged into a blending tank equipped with stirring blades, heated if necessary, and stirred to make it uniform.

  Although the usage form of the oil agent of the present invention is not particularly limited, it is usually an emulsion or a low-viscosity mineral oil (for example, liquid paraffin having a kinematic viscosity of 1 to 10 cst at 25 ° C.) or a solvent (for example, methanol, ethanol, isopropanol, acetone). , Methyl ethyl ketone, diethyl ether, benzene, toluene, xylene, etc.) or the like. More preferably it is used as an emulsion. When used as an emulsion, the method for preparing the emulsion is not particularly limited. For example, a method in which a predetermined amount of ion-exchanged water is put into an emulsification tank and the oil agent of the present invention is gradually added and emulsified with stirring can be applied. . The concentration of the emulsion is usually 5 to 40% by weight, preferably 8 to 30% by weight. The emulsification temperature is usually 10 to 60 ° C.

  The oil agent of the present invention can be supplied at any position in the spinning process, but is usually supplied to a non-stretched fiber immediately after spinning by a predetermined amount. Arbitrary well-known methods, such as a roller and a nozzle, are applicable for the oil supply method. After the fiber is refueled, it is drawn and wound. Although the adhesion amount with respect to the fiber of the oil agent of this invention is not specifically limited, Usually, 0.05-8 weight% as an oil agent pure part with respect to a fiber, Preferably it is 0.1-5 weight%.

  The synthetic fiber to which the oil agent of the present invention can be applied is not particularly limited, and can be applied to polyester, polyamide, polyacryl, polylactic acid, rayon, acetate and the like, and exhibits excellent effects.

  The use of the synthetic fiber treated with the oil agent of the present invention is not particularly limited, and can be widely used for various garments, industrial materials, etc. in various forms such as woven fabrics and knitted fabrics.

<Example>
EXAMPLES Hereinafter, although an Example is given and the structure and effect of this invention are further explained in full detail, this invention is not limited to these Examples.

[Catalyst synthesis example-1]
A reaction vessel equipped with a stirrer and a thermometer was charged with 114 parts by weight (0.5 mol) of tetraethoxide titanate. While stirring at 40 to 45 ° C., 146 parts by weight (1.0 mol) of adipic acid was gradually added thereto. The reaction was continued while the generated ethanol was removed under reduced pressure, and the whole amount was added over 1 hour. The reaction was continued while reducing the pressure at the same temperature for another 2 hours after the entire amount was added, and when the ethanol flow was stopped, the reaction was terminated, and 168 parts by weight of diethoxytitanate-bis (adipic acid) complex (ca) Got.
[Catalyst synthesis example-2]
Using the same apparatus as in Synthesis Example 1, 142 parts by weight (0.5 mol) of tetraisopropoxytitanate was added, and 100 parts by weight (1.0 mol) of acetylacetone was gradually added dropwise with stirring at 50 to 55 ° C. did. The reaction was continued while the generated isopropanol was removed under reduced pressure, and the whole amount was charged over 45 minutes. The reaction was continued while reducing the pressure at the same temperature for another hour after the entire amount was added, and when the outflow of isopropanol was no longer observed, the reaction was terminated, and 122 parts by weight of diisopropoxytitanate-bis (acetylacetone) complex (cb) Got.
[Catalyst synthesis example-3]
Using the same apparatus as in Synthesis Example-1, 170 parts by weight (0.5 mol) of tetrabutoxytitanate was charged, and 176 parts by weight (1.0 mol) of ethylenediaminediacetic acid was gradually added while stirring at 60 to 65 ° C. I put it in. The reaction was continued while the generated butanol was removed under reduced pressure, and the whole amount was added over 1 hour 30 minutes. The reaction was continued while reducing the pressure at the same temperature for 2 hours after the entire amount was added, and when no butanol flow was observed, the reaction was terminated, and 198 parts by weight of dibutoxy titanate-bis (ethylenediaminediacetic acid) complex (cc) Got.

[Synthesis Example 1] <Synthesis of ester compound (A-1)>
A reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 130 parts by weight of octyl alcohol and 280 parts by weight of isostearic acid (reaction molar ratio is octyl alcohol: isostearic acid = 1: 1). To this, 0.1 wt% of (ca) was added as an esterification catalyst with respect to isostearic acid. The temperature was raised to 150 ° C. while blowing nitrogen into the liquid, and esterification was performed at 150 to 155 ° C. at normal pressure while exhausting nitrogen out of the reaction vessel. The progress of esterification was confirmed by measuring the acid value, and the reaction was continued until the acid value became 1 or less to obtain an ester compound (A-1) octyl isostearate. The reaction time was 1.5 hours. The obtained (A-1) had a good appearance without coloring, and was used in the examples as it was without removing the catalyst.

[Synthesis Example 2] <Ester Compound (A-2)>
In the same apparatus as in Synthesis Example 1, 200 parts by weight of lauryl alcohol and 73 parts by weight of adipic acid (reaction molar ratio: lauryl alcohol: adipic acid = 2: 1) were charged. To this, 0.3 wt% of (cb) was added as an esterification catalyst with respect to adipic acid. The temperature was raised to 170 ° C. while blowing nitrogen into the liquid, and esterification was performed at 170 to 175 ° C. at normal pressure while exhausting nitrogen out of the reaction vessel. The progress of esterification was confirmed by measuring the acid value, and the reaction was continued until the acid value became 1 or less to obtain an ester compound (A-2) dilauryl adipate. The reaction time was 4 hours. The obtained (A-2) had a good appearance without coloring, and was used in the examples as it was without removing the catalyst.

[Synthesis Example 3] <Ester compound (A-3)>
In the same apparatus as in Synthesis Example 1, 130 parts by weight of 2-ethylhexanol and 280 parts by weight of oleic acid (reaction molar ratio: 2-ethylhexanol: oleic acid = 1: 1) were charged. As an esterification catalyst, 0.2% by weight of (c-c) was added to stearic acid. While nitrogen was blown into the liquid, the temperature was raised to 140 ° C., and esterification was performed at 140 to 145 ° C. at normal pressure while exhausting nitrogen out of the reaction vessel. Confirmation of the progress of esterification was performed by measuring the acid value, and the reaction was continued until the acid value became 0.5 or less to obtain ester compound (A-3) 2-ethylhexyl oleate. The reaction time was 5 hours. The obtained (A-3) had a good appearance without coloration, and was used in the examples as it was without removing the catalyst.

[Synthesis Example 4] <Ester compound (A-4)>
In the same apparatus as in Synthesis Example 1, 280 parts by weight of oleyl alcohol and 280 parts by weight of oleic acid (reaction molar ratio: oleyl alcohol: oleic acid = 1: 1) were charged. As an esterification catalyst, 0.8% by weight of (cc) was added to oleic acid. While nitrogen was blown into the liquid, the temperature was raised to 140 ° C., and esterification was performed at 140 to 145 ° C. at normal pressure while exhausting nitrogen out of the reaction vessel. Confirmation of the progress of esterification was performed by measuring the acid value, and the reaction was continued until the acid value became 0.5 or less to obtain an ester compound (A-4) oleyl oleate. The reaction time was 6 hours. The obtained (A-4) had a good appearance without coloration and was used in the examples as it was without removing the catalyst.

[Comparative Synthesis Example 1] <Comparative ester compound (E-1)>
In Synthesis Example 1, a comparative ester compound (E-1) octyl isostearate was obtained in the same manner except that paratoluenesulfonic acid was used in place of (ca) as the esterification catalyst. The reaction time was 6 hours. The obtained (E-1) was neutralized with potassium hydroxide, treated with an adsorbent, and used in the examples.
[Comparative Synthesis Example 2] <Comparative ester compound (E-2)>
A comparative ester compound (E-2) dilauryl adipate was obtained in the same manner as in Synthesis Example 2 except that paratoluenesulfonic acid was used instead of (c-b) as the esterification catalyst. The reaction time was 7 hours. The obtained (E-2) was neutralized with potassium hydroxide, treated with an adsorbent, and used in the examples.
[Comparative Synthesis Example 3] <Comparative ester compound (E-3)>
In Synthesis Example 3, a comparative ester compound (E-3) 2-ethylhexyl oleate was obtained in the same manner except that p-toluenesulfonic acid was used instead of (cc) as the esterification catalyst. The reaction time was 7 hours. The obtained (E-3) was neutralized with potassium hydroxide, treated with an adsorbent, and used in the examples.
[Comparative Synthesis Example 4] <Comparative ester compound (E-4)>
A comparative ester compound (E-4) oleyl oleate was obtained in the same manner as in Synthesis Example 4 except that paratoluenesulfonic acid was used in place of (c-c) as the esterification catalyst. The reaction time was 8 hours. The obtained (E-4) was neutralized with potassium hydroxide, treated with an adsorbent, and used in the examples.

[Example]
Using the ester compound and the following components, oil agents 1 to 7 and comparative oil agents 1 to 6 of the present invention were blended as shown in Table 1.
(B1-1) Isostearyl alcohol EO 5 mol adduct (B1-2) Butanol EO / PO random adduct (Mw = 2,500)
(B1-3) sorbitol dilaurate EO 30 mol adduct (B1-4) hydrogenated castor oil EO 12 mol adduct (C1-1) 2-ethylhexanol EO3 mol adduct (C1-2) 2-ethylhexanol EO 7 mol adduct ( D-1) Mineral oil (Redwood 100 seconds)
(D-2) Refined coconut oil (D-3) Lauric acid diethanolamide (D-4) Stearylamine EO 15 mol adduct (D-5) Lauryl phosphate potassium salt (D-6) Oleic acid soap (D-7 ) Sodium lauryl sulfonate

The following evaluation was performed using these. The results are shown in Table 2.
<Evaluation items and evaluation methods>
<Lubricity>
Each oil agent is attached to polyester filament yarn (83 dtex, 36 filament) so that the amount of attachment is 1.0% by weight, and a metal pin (surface textured finish) by running yarn method with initial tension of 20 g and yarn speed of 100 m / min. The tension (g) after passing through the metal pin was measured to obtain lubricity. It shows that lubricity is so favorable that a value is small.
<Heat resistance>
1.0 g of each oil was taken in a stainless steel petri dish (diameter 5 cm) and left in a dryer at 150 ° C. for 8 hours. The state of the oil agent in the petri dish after being left was visually observed to judge the heat resistance.
○ ... Good heat resistance (less coloring. No tar generation)
Δ: Heat resistance is slightly poor (slightly colored. Some tar is generated)
× ... Poor heat resistance (strong coloring, frequent tar generation)
<Electricity generated>
The amount of electricity generated at 10 cm above the metal pin when evaluating the lubricity was measured with a potentiometer (manufactured by Kasuga Electric). The larger the absolute value, the greater the amount of electricity generated.

  Furthermore, using the oil agent of the present invention and the comparative oil agent shown in Table 1, a 12% active ingredient emulsion was prepared and applied to the unstretched polyester yarn immediately after spinning using a spinning machine so that the adhesion amount was 1.0% by weight. Then, the film was drawn and wound at a winding speed of 6,000 m / min. The yarn thickness after winding was 85 dtex (number of filaments: 12). Table 3 shows the results of observing the number of yarn breaks per 24 hours and the fluff state of the wound cheese for each oil.

  From Tables 2 and 3, it is clear that the oil agent of the present invention has good lubricity, heat resistance and antistatic properties, good yarn-making properties, and extremely excellent yarn quality.

  Since the oil agent of the present invention is excellent in lubricity, heat resistance, and antistatic properties, troubles such as yarn breakage and fluff can be reduced in the spinning process, and very good yarn forming properties are provided. Moreover, the quality of the fiber obtained is also excellent, and it is suitable as an oil agent for synthetic fibers.

Claims (7)

  Using metal complex (c) formed from chelating agent (c1) and titanate compound (c2) as a catalyst, carboxylic acid (a1) and / or its ester-forming derivative (a2) and alcohol (b) are reacted. An oil agent for synthetic fibers, characterized by comprising an ester compound (A) obtained by mixing, an emulsifier component (B), and a wetting component (C). The oil according to claim 1, wherein (c1) is a compound represented by the following general formula (1).
[Wherein, X is a group represented by -OM or a hydrocarbon group having 1 to 30 carbon atoms, and some hydrogen atoms may be substituted with halogen atoms; M is a hydrogen atom or an alkali metal atom Y is a hydrocarbon group having 1 to 14 carbon atoms which may contain a nitrogen atom; X may be the same or different. The oil according to claim 1 or 2, wherein (c2) is a compound represented by the following general formula (2).
[In the formula, L is a group represented by R ¹ , R ¹ O— or R ¹ S—, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, and part of the hydrogen atoms are substituted with halogen atoms. May be]   The oil agent according to any one of claims 1 to 3, wherein a molar ratio of (c1) to (c2) is (c1) / (c2) = 1/4 to 4/1. L is oil according to any of claims 1 to 4 R ¹ O-a is of the general formula (2).   In the synthetic fiber spinning process, after processing a fiber using the oil agent in any one of Claims 1-5, extending | stretching and winding up, The processing method of the synthetic fiber characterized by the above-mentioned. A synthetic fiber treated by the method according to claim 6.